JP6190023B1 - Method for producing zirconium tungstate phosphate - Google Patents
Method for producing zirconium tungstate phosphate Download PDFInfo
- Publication number
- JP6190023B1 JP6190023B1 JP2016193026A JP2016193026A JP6190023B1 JP 6190023 B1 JP6190023 B1 JP 6190023B1 JP 2016193026 A JP2016193026 A JP 2016193026A JP 2016193026 A JP2016193026 A JP 2016193026A JP 6190023 B1 JP6190023 B1 JP 6190023B1
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- zirconium
- compound
- reaction precursor
- tungstate phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 45
- OJLGWNFZMTVNCX-UHFFFAOYSA-N dioxido(dioxo)tungsten;zirconium(4+) Chemical compound [Zr+4].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O OJLGWNFZMTVNCX-UHFFFAOYSA-N 0.000 title claims abstract description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 44
- 239000010452 phosphate Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- 239000002243 precursor Substances 0.000 claims abstract description 71
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims description 136
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 80
- 238000000034 method Methods 0.000 claims description 47
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 46
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 28
- 150000003755 zirconium compounds Chemical class 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 20
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 9
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000001238 wet grinding Methods 0.000 claims 1
- 238000002441 X-ray diffraction Methods 0.000 abstract description 33
- 239000000463 material Substances 0.000 abstract description 20
- 235000021317 phosphate Nutrition 0.000 description 29
- 239000002270 dispersing agent Substances 0.000 description 20
- 239000011324 bead Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 14
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 150000003863 ammonium salts Chemical class 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 11
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007561 laser diffraction method Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000000790 scattering method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 3
- 239000004137 magnesium phosphate Substances 0.000 description 3
- 229960002261 magnesium phosphate Drugs 0.000 description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 3
- 235000010994 magnesium phosphates Nutrition 0.000 description 3
- -1 organic acid salts Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/36—Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
- C04B14/366—Phosphates, e.g. apatite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/008—Cement and like inorganic materials added as expanding or shrinkage compensating ingredients in mortar or concrete compositions, the expansion being the result of a recrystallisation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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Abstract
【課題】負熱膨張材として有用なX線回折的に単相のリン酸タングステン酸ジルコニウムを工業的に有利な方法で得る方法の提供。【解決手段】タングステン化合物、リン、ジルコニウムを含む不定形化合物の混合物を反応前駆体とし、該反応前駆体を焼成することを特徴とする。前記反応前駆体は、少なくとも950〜1150cm-1に赤外線吸収ピークを有し、この範囲での赤外線吸収ピークの極大値が1030(±20)cm-1にあることが好ましい。【選択図】図6An object of the present invention is to provide an X-ray diffraction single phase zirconium tungstate phosphate useful as a negative thermal expansion material in an industrially advantageous manner. A mixture of an amorphous compound containing a tungsten compound, phosphorus, and zirconium is used as a reaction precursor, and the reaction precursor is calcined. The reaction precursor has an infrared absorption peak at least in the range of 950 to 1150 cm <-1>, and the maximum value of the infrared absorption peak in this range is preferably 1030 (± 20) cm <-1>. [Selection] Figure 6
Description
本発明は、負熱膨張材として有用なリン酸タングステン酸ジルコニウムの製造方法に関するものである。 The present invention relates to a method for producing zirconium tungstate phosphate useful as a negative thermal expansion material.
多くの物質は温度が上昇すると、熱膨張によって長さや体積が増大する。これに対して、温めると逆に体積が小さくなる負の熱膨張を示す材料(「負熱膨張材」ということもある)も知られている。負の熱膨張を示す材料は、他の材料と共に用いて、温度変化による材料の熱膨張の変化を抑制することが出来ることが知られている。 Many materials increase in length and volume due to thermal expansion as the temperature increases. On the other hand, a material exhibiting negative thermal expansion (which may be referred to as a “negative thermal expansion material”) whose volume decreases conversely when heated is also known. It is known that a material exhibiting negative thermal expansion can be used together with other materials to suppress a change in thermal expansion of the material due to a temperature change.
負の熱膨張を示す材料としては、例えば、β−ユークリプタイト、タングステン酸ジルコニウム(ZrW2O8)、リン酸タングステン酸ジルコニウム(Zr2WO4(PO4)2)、ZnxCd1-x(CN)2、マンガン窒化物、ビスマス・ニッケル・鉄酸化物等が知られている。 Examples of the material exhibiting negative thermal expansion include β-eucryptite, zirconium tungstate (ZrW 2 O 8 ), zirconium phosphate tungstate (Zr 2 WO 4 (PO 4 ) 2 ), Zn x Cd 1- x (CN) 2 , manganese nitride, bismuth / nickel / iron oxide and the like are known.
リン酸タングステン酸ジルコニウムの線膨張係数は、0〜400℃の温度範囲で、−3.4〜−3.0ppm/℃であり負熱膨張性が大きく、正の熱膨張を示す材料と併用して用いることで低熱膨張の材料を製造することが出来る。 The coefficient of linear expansion of zirconium phosphate tungstate is −3.4 to −3.0 ppm / ° C. in the temperature range of 0 to 400 ° C., and has a large negative thermal expansion property. Can be used to produce a low thermal expansion material.
リン酸タングステン酸ジルコニウムの製造方法としては、例えば、下記特許文献1には、結晶性のリン酸ジルコニウム、酸化タングステン及びMgO等の反応促進剤を湿式ボールミルで混合し、得られる混合物を1200℃で焼成する方法、下記特許文献2には、リン酸アンモニウム等のリン源と、タングステン酸アンモニウム等のタングステン源及び塩化ジルコニウム等のジルコニウム源を湿式混合した後、仮焼する方法、下記非特許文献1には、酸化ジルコニウム、酸化タングステンとリン酸二水素アンモニウムを含む混合物を1200℃で焼成する方法等が提案されている。 As a method for producing zirconium tungstate phosphate, for example, in Patent Document 1 below, a reaction accelerator such as crystalline zirconium phosphate, tungsten oxide and MgO is mixed in a wet ball mill, and the resulting mixture is 1200 ° C. In the method of firing, Patent Document 2 below, a phosphorus source such as ammonium phosphate, a tungsten source such as ammonium tungstate, and a zirconium source such as zirconium chloride are wet-mixed and then calcined, Non-Patent Document 1 below. Proposed a method of firing a mixture containing zirconium oxide, tungsten oxide and ammonium dihydrogen phosphate at 1200 ° C.
負熱膨張材としてリン酸タングステン酸ジルコニウムは、超精密加工のための部材として有望視され、更に工業的に有利な方法で、リン酸タングステン酸ジルコニウムを得る方法の開発も要望されている。 Zirconium tungstate phosphate as a negative thermal expansion material is considered promising as a member for ultraprecision machining, and further development of a method for obtaining zirconium tungstate phosphate by an industrially advantageous method is also desired.
従って、本発明の目的は、工業的に有利な方法で、負熱膨張材として有用なX線回折的に単相のリン酸タングステン酸ジルコニウムを得る方法を提供することにある。 Accordingly, an object of the present invention is to provide a method of obtaining X-ray diffraction single phase zirconium phosphate tungstate useful as a negative thermal expansion material in an industrially advantageous manner.
本発明者らは、上記実情に鑑み鋭意研究を重ねた結果、水に不溶性ないし難溶性のタングステン化合物の存在下に、リン酸と特定のジルコニウム化合物との反応を行って得られるタングステン化合物と、リンとジルコニウムを含む無定形の化合物との混合物は反応性に優れた反応前駆体となり、この反応前駆体を用いることにより容易にX線回折的に単相のリン酸タングステン酸ジルコニウムが得られることを見出し、本発明を完成するに到った。 As a result of intensive studies in view of the above circumstances, the present inventors have obtained a tungsten compound obtained by reacting phosphoric acid with a specific zirconium compound in the presence of a water-insoluble or hardly soluble tungsten compound, A mixture of phosphorus and an amorphous compound containing zirconium becomes a reaction precursor having excellent reactivity, and by using this reaction precursor, single-phase zirconium tungstate phosphate can be easily obtained by X-ray diffraction. As a result, the present invention has been completed.
即ち、本発明が提供しようとするリン酸タングステン酸ジルコニウムの製造方法は、タングステン化合物と、リンとジルコニウムを含む無定形の化合物との混合物を反応前駆体として、該反応前駆体を焼成することを特徴とするものである。 That is, the method for producing zirconium tungstate phosphate to be provided by the present invention includes firing a reaction precursor using a mixture of a tungsten compound and an amorphous compound containing phosphorus and zirconium as a reaction precursor. It is a feature.
本発明によれば、工業的に有利な方法で、負熱膨張材として有用なX線回折的に単相のリン酸タングステン酸ジルコニウムを得ることができる。 According to the present invention, an X-ray diffraction single phase zirconium tungstate phosphate useful as a negative thermal expansion material can be obtained by an industrially advantageous method.
以下、本発明をその好ましい実施形態に基づいて説明する。
本発明のリン酸タングステン酸ジルコニウムの製造方法は、タングステン化合物と、リンとジルコニウムを含む不定形の化合物との混合物を反応前駆体として、該反応前駆体を焼成することを特徴とするものである。
Hereinafter, the present invention will be described based on preferred embodiments thereof.
The method for producing zirconium tungstate phosphate of the present invention is characterized in that the reaction precursor is fired using a mixture of a tungsten compound and an amorphous compound containing phosphorus and zirconium as a reaction precursor. .
本発明者らは、リン酸とジルコニウム化合物との反応により得られるリンとジルコニウムを含む無定形の化合物は、微細な一次粒子であり、所望のモル比でリン原子とジルコニウム原子を含むものであること。また、タングステン化合物が均一に分散したスラリー中で、かかる反応を行うことで、タングステン化合物と、リンとジルコニウムを含む無定形の化合物とが均一分散したスラリーが得られること。更に、これを乾燥処理すると各原料が均一に分散し、所望のモル比でZr、W、Pを含んだ反応性に優れた反応前駆体になることを見出した。 The present inventors indicate that the amorphous compound containing phosphorus and zirconium obtained by the reaction of phosphoric acid and a zirconium compound is a fine primary particle and contains phosphorus atoms and zirconium atoms in a desired molar ratio. In addition, by performing such a reaction in a slurry in which a tungsten compound is uniformly dispersed, a slurry in which the tungsten compound and an amorphous compound containing phosphorus and zirconium are uniformly dispersed is obtained. Furthermore, it has been found that when this is dried, each raw material is uniformly dispersed, and a reactive precursor containing Zr, W, and P in a desired molar ratio is obtained.
例えば、ジルコニウム化合物として水酸化ジルコニウムを用いた場合、得られる反応前駆体をX線回折分析したときに、タングステン化合物のみの回折ピークが確認され(図1参照。)、水酸化ジルコニウムの回折ピークは観察されない。また、該反応前駆体をFT−IR分析したときに、水酸化ジルコニウムとリン酸とは異なる赤外線吸収ピークのパターンを示す(図2参照。)ことから、スラリーへ添加した水酸化ジルコニウムとリン酸は、反応していることが確認できる。 For example, when zirconium hydroxide is used as the zirconium compound, a diffraction peak of only the tungsten compound is confirmed when the obtained reaction precursor is analyzed by X-ray diffraction (see FIG. 1). Not observed. Further, when the reaction precursor is subjected to FT-IR analysis, it shows an infrared absorption peak pattern different from that of zirconium hydroxide and phosphoric acid (see FIG. 2). Therefore, zirconium hydroxide and phosphoric acid added to the slurry are shown. Can be confirmed to have reacted.
なお、本発明者らは、リン酸とジルコニウム化合物との反応により得られるリンとジルコニウムを含む無定形の化合物は、無定形のリン酸ジルコニウムであると推測している。 Note that the present inventors presume that the amorphous compound containing phosphorus and zirconium obtained by the reaction of phosphoric acid and a zirconium compound is amorphous zirconium phosphate.
本製造方法において、前記反応前駆体は、少なくとも950〜1150cm-1に赤外線吸収ピークを有し、この範囲での赤外線吸収ピークの極大値が1030(±20)cm-1にあるものが好ましい。 In this manufacturing method, the reaction precursor has an infrared absorption peak at least 950~1150Cm -1, which maximum value of the infrared absorption peak in this range is in the 1030 (± 20) cm -1 are preferred.
また、前記反応前駆体中のZr、W、Pのモル比は、Zr/W=1.7〜2.3、好ましくは1.9〜2.1であり、P/W=1.7〜2.3、好ましくは1.9〜2.1である。 The molar ratio of Zr, W, and P in the reaction precursor is Zr / W = 1.7 to 2.3, preferably 1.9 to 2.1, and P / W = 1.7 to 2.3, preferably 1.9 to 2.1.
本発明において、前記反応前駆体は、下記の2つの方法で得られるものが好ましい。
(1)タングステン化合物を含むスラリーを調製する第一工程、次いで該スラリーにリン酸と、水酸化ジルコニウム及び炭酸ジルコニウムから選ばれるジルコニウム化合物を添加する第二工程、次いで得られるスラリーを全量乾燥する第3工程を含む方法(以下、「第1の方法」と言う)。
(2)タングステン化合物、リン源及びジルコニウム源を含むスラリーを加熱処理する第A工程、次いで、該スラリーをメディアミルで湿式粉砕処理する第B工程、次いで得られるスラリーを全量乾燥する第C工程を含む方法(以下、「第2の方法」と言う)。
In the present invention, the reaction precursor is preferably obtained by the following two methods.
(1) A first step of preparing a slurry containing a tungsten compound, then a second step of adding phosphoric acid and a zirconium compound selected from zirconium hydroxide and zirconium carbonate to the slurry, and then drying the resulting slurry in its entirety. A method including three steps (hereinafter referred to as “first method”).
(2) Step A in which a slurry containing a tungsten compound, a phosphorus source and a zirconium source is heat-treated, then Step B in which the slurry is subjected to wet pulverization with a media mill, and then Step C in which the resulting slurry is completely dried Including method (hereinafter referred to as “second method”).
<第1の方法>
以下、第1の方法で前記反応前駆体を製造する方法について説明する。
<First method>
Hereinafter, a method for producing the reaction precursor by the first method will be described.
第1の方法に係る第一工程は、タングステン化合物が分散媒体となる水溶媒に均一に分散したスラリーを調製する工程である。 The first step according to the first method is a step of preparing a slurry in which a tungsten compound is uniformly dispersed in an aqueous solvent serving as a dispersion medium.
第一工程に係るタングステン化合物は、水に対して不溶性ないし難溶性の化合物が好ましく、例えば、三酸化タングステン、タングステン酸アンモニウム、塩化タングステン等のタングステン化合物が挙げられる。これらのうち、三酸化タングステンが純度が高いものが工業的に容易に入手でき、また取扱いも容易であるという観点から好ましい。 The tungsten compound according to the first step is preferably a compound that is insoluble or hardly soluble in water, and examples thereof include tungsten compounds such as tungsten trioxide, ammonium tungstate, and tungsten chloride. Among these, tungsten trioxide having a high purity is preferable from the viewpoint of being easily available industrially and easy to handle.
用いることが出来るタングステン化合物の好ましい物性は、レーザー回折・散乱法に求められる平均粒子径が100μm以下、好ましくは0.1〜50μmであることが、反応性が優れた反応前駆体を得る観点から好ましい。 The preferred physical properties of the tungsten compound that can be used are that the average particle size required for the laser diffraction / scattering method is 100 μm or less, preferably 0.1 to 50 μm, from the viewpoint of obtaining a reaction precursor with excellent reactivity. preferable.
第一工程に係るタングステン化合物を分散させる溶媒は、水だけに限らず水と親水性溶媒との混合溶媒であってもよい。
第一工程に係るスラリー濃度は5〜50質量%、好ましくは10〜30質量%とすることが操作性と取扱いが容易な粘度のスラリーとなる観点から好ましい。
The solvent for dispersing the tungsten compound according to the first step is not limited to water but may be a mixed solvent of water and a hydrophilic solvent.
The slurry concentration in the first step is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass from the viewpoint of providing a slurry with a viscosity that is easy to handle and handle.
第一工程は、レーザー回折・散乱法により求められる固形分の平均粒子径が5μm以下、好ましくは2μm以下のスラリーを調製することが反応性に優れた反応前駆体を得る観点から好ましい。 In the first step, it is preferable from the viewpoint of obtaining a reaction precursor excellent in reactivity to prepare a slurry having an average particle size of solids determined by a laser diffraction / scattering method of 5 μm or less, preferably 2 μm or less.
第一工程において、タングステン化合物を水溶媒に均一分散させる方法としては、タングステン化合物を水溶媒中に均一分散できる手段であれば特に制限なく用いることが出来るが、タングステン化合物の粒子は、凝集性が特に強いことから、分散剤をスラリーに添加する方法であってもよいが、固形分の平均粒子径が上記範囲となるように粉砕と分散を同時に行えるメディアミルによる湿式粉砕処理により行うことが一層反応性に優れた反応前駆体を得る観点から特に好ましい。 In the first step, as a method for uniformly dispersing the tungsten compound in the aqueous solvent, any means that can uniformly disperse the tungsten compound in the aqueous solvent can be used without any particular limitation. Since it is particularly strong, it may be a method of adding a dispersant to the slurry, but it is further carried out by a wet pulverization process by a media mill capable of simultaneously pulverizing and dispersing so that the average particle size of the solid content is in the above range. This is particularly preferable from the viewpoint of obtaining a reaction precursor having excellent reactivity.
使用する分散剤は、分散媒の種類に応じて適切なものを選択すればよい。分散媒が例えば水である場合には、分散剤として各種の界面活性剤、ポリカルボン酸アンモニウム塩等を用いることができる。スラリーにおける分散剤の濃度は0.01〜10重量%、特に0.1〜5重量%とすることが、分散効果が高くなる観点で好ましい。 What is necessary is just to select a suitable dispersing agent to use according to the kind of dispersion medium. When the dispersion medium is water, for example, various surfactants, polycarboxylic acid ammonium salts, and the like can be used as the dispersant. The concentration of the dispersant in the slurry is preferably 0.01 to 10% by weight, particularly 0.1 to 5% by weight from the viewpoint of increasing the dispersion effect.
メディアミルとしては、ビーズミル、ボールミル、ペイントシェーカー、アトライタ、サンドミル等を用いることができる。特にビーズミルを用いることが好ましい。その場合、運転条件やビーズの種類及び大きさは、装置のサイズや処理量に応じて適切に選択すればよい。 As the media mill, a bead mill, a ball mill, a paint shaker, an attritor, a sand mill, or the like can be used. It is particularly preferable to use a bead mill. In that case, the operating conditions and the type and size of the beads may be appropriately selected according to the size of the apparatus and the processing amount.
メディアミルを用いた処理を一層効率的に行う観点から、スラリーに、分散剤を加えてもよい。使用する分散剤は、分散媒の種類に応じて適切なものを選択すればよい。分散媒が例えば水である場合には、分散剤として各種の界面活性剤、ポリカルボン酸アンモニウム塩等を用いることができる。スラリーにおける分散剤の濃度は0.01〜10重量%、特に0.1〜5重量%とすることが、分散効果が高くなる観点で好ましい。 From the viewpoint of more efficiently performing the treatment using the media mill, a dispersant may be added to the slurry. What is necessary is just to select a suitable dispersing agent to use according to the kind of dispersion medium. When the dispersion medium is water, for example, various surfactants, polycarboxylic acid ammonium salts, and the like can be used as the dispersant. The concentration of the dispersant in the slurry is preferably 0.01 to 10% by weight, particularly 0.1 to 5% by weight from the viewpoint of increasing the dispersion effect.
メディアミルを用いた粉砕処理は、レーザー回折・散乱法により求められる固形分の平均粒子径が1μm以下、好ましくは0.1〜1μmとなるまで行うと一層反応性に優れた反応前駆体を得ることができる観点から好ましい。
かくすることにより、タングステン化合物が水溶媒中に均一分散したスラリーを調製することができる。
When the pulverization treatment using a media mill is carried out until the average particle size of the solid content determined by the laser diffraction / scattering method is 1 μm or less, preferably 0.1 to 1 μm, a reaction precursor with even higher reactivity is obtained. From the viewpoint of being able to do so.
Thus, a slurry in which the tungsten compound is uniformly dispersed in the aqueous solvent can be prepared.
次いで、第二工程で、第一工程で得られたスラリーにリン酸と、水酸化ジルコニウム及び炭酸ジルコニウムから選ばれるジルコニウム化合物(以下、単に「ジルコニウム化合物」と言うことがある)を添加して反応前駆体を調製する。 Next, in the second step, phosphoric acid and a zirconium compound selected from zirconium hydroxide and zirconium carbonate (hereinafter sometimes simply referred to as “zirconium compound”) are added to the slurry obtained in the first step and reacted. A precursor is prepared.
第二工程では、タングステン化合物の存在下に、リン酸とジルコニウム化合物との反応を行うことにより、タングステン化合物と、リンとジルコニウムを含む無定形の化合物との混合物を含むスラリーを得る。 In the second step, a slurry containing a mixture of a tungsten compound and an amorphous compound containing phosphorus and zirconium is obtained by reacting phosphoric acid with a zirconium compound in the presence of the tungsten compound.
第二工程に係るリン酸は、工業的に入手できるものであれば、特に制限なく用いることができ、また、リン酸はリン酸水溶液として第一工程で得られるスラリーに添加することができる。 If the phosphoric acid which concerns on a 2nd process can be obtained industrially, it can be especially used without a restriction | limiting, and phosphoric acid can be added to the slurry obtained at a 1st process as phosphoric acid aqueous solution.
第二工程に係るジルコニウム化合物は、水酸化ジルコニウム及び/又は炭酸ジルコニウムである。
炭酸ジルコニウムは、塩基性塩であってもよく、アンモニアやナトリウム、カリウムなどの複塩であってもよい。
ジルコニウム化合物は、工業的に入手できるものであれば、特に制限なく用いることができ、また、ジルコニウム化合物は無水塩又は含水塩であってもよい。
ジルコニウム化合物は、そのまま粉体として第一工程で得られるスラリーに添加することができるが、水溶媒に分散させた懸濁液もしくは溶解させた溶液として添加してもよい。
The zirconium compound according to the second step is zirconium hydroxide and / or zirconium carbonate.
Zirconium carbonate may be a basic salt or a double salt such as ammonia, sodium or potassium.
The zirconium compound can be used without particular limitation as long as it is industrially available, and the zirconium compound may be an anhydrous salt or a hydrated salt.
The zirconium compound can be added as a powder to the slurry obtained in the first step as it is, but it may be added as a suspension dispersed in an aqueous solvent or a dissolved solution.
リン酸のスラリーへの添加量は、スラリー中のタングステン化合物中のW元素に対するリン酸中のP元素のモル比(P/W)で1.7〜2.3、好ましくは1.9〜2.1とすることが負の熱膨張が大きなものが得られるという観点から好ましい。 The amount of phosphoric acid added to the slurry is 1.7 to 2.3, preferably 1.9 to 2, in terms of the molar ratio (P / W) of P element in phosphoric acid to W element in the tungsten compound in the slurry. .1 is preferable from the viewpoint that a negative thermal expansion can be obtained.
ジルコニウム化合物のスラリーへの添加量は、スラリー中のタングステン化合物中のW元素に対するジルコニウム化合物中のZr元素のモル比(Zr/W)で1.7〜2.3、好ましくは1.9〜2.1とすることが負の熱膨張が大きなものが得られるという観点から好ましい。 The addition amount of the zirconium compound to the slurry is 1.7 to 2.3, preferably 1.9 to 2 in terms of the molar ratio (Zr / W) of the Zr element in the zirconium compound to the W element in the tungsten compound in the slurry. .1 is preferable from the viewpoint that a negative thermal expansion can be obtained.
また、スラリーに添加するタングステン化合物とリン酸の配合割合は、タングステン化合物中のW元素に対するリン酸中のP元素のモル比(P/W)で1.7〜2.3、好まし
くは1.9〜2.1とすることが負の熱膨張が大きなものが得られるという観点から好ましい。
Moreover, the compounding ratio of the tungsten compound and phosphoric acid added to the slurry is 1.7 to 2.3, preferably 1. in terms of the molar ratio (P / W) of P element in phosphoric acid to W element in the tungsten compound. It is preferable to set it to 9-2.1 from a viewpoint that a thing with a large negative thermal expansion is obtained.
スラリー中でのリン酸とジルコニウム化合物との反応条件は、反応温度が5〜100℃、好ましくは10〜50℃とすることが操作性と取扱いが容易な粘度のスラリーとなる観点から好ましい。 The reaction conditions of phosphoric acid and the zirconium compound in the slurry are preferably 5 to 100 ° C., more preferably 10 to 50 ° C., from the viewpoint of obtaining a slurry with a viscosity that is easy to handle and handle.
第二工程での反応時間は本製造方法において臨界的ではなく、リンとジルコニウムを含む無定形の化合物が生成するまで十分な時間反応を行えばよい。多くの場合、0.5時間以上、好ましくは1〜4時間で、満足の行く諸物性のタングステン化合物と、リンとジルコニウムを含む無定形の化合物が均一分散したスラリーを生成させることが出来る。 The reaction time in the second step is not critical in the present production method, and the reaction may be performed for a sufficient time until an amorphous compound containing phosphorus and zirconium is produced. In many cases, a slurry in which a satisfactory tungsten compound having various physical properties and an amorphous compound containing phosphorus and zirconium are uniformly dispersed can be produced in 0.5 hours or longer, preferably 1 to 4 hours.
反応終了後、第2工程後のスラリーは固液分離せずに、第3工程で該スラリーを全量乾燥することで、第1の方法で本発明で使用する反応前駆体を得ることができる。スラリーを全量乾燥する方法として、特に制限されるものではないが、噴霧乾燥により乾燥処理を行うと原料粒子が密に詰まった状態の造粒物が得られることから、より一層粉末X線回折的には単相のリン酸タングステン酸ジルコニウムが得やすくなる観点から好ましい。 After completion of the reaction, the slurry after the second step is not subjected to solid-liquid separation, and the slurry is completely dried in the third step, whereby the reaction precursor used in the present invention can be obtained by the first method. The method for drying the entire slurry is not particularly limited, but if a drying process is performed by spray drying, a granulated product in which raw material particles are densely packed is obtained. Is preferable from the viewpoint of easily obtaining single-phase zirconium tungstate phosphate.
噴霧乾燥法においては、所定手段によってスラリーを霧化し、それによって生じた微細な液滴を乾燥させることで反応前駆体を得る。スラリーの霧化には、例えば回転円盤を用いる方法と、圧力ノズルを用いる方法がある。第3工程においてはいずれの方法も用いることもできる。 In the spray-drying method, the reaction precursor is obtained by atomizing the slurry by a predetermined means and drying fine droplets generated thereby. The atomization of the slurry includes, for example, a method using a rotating disk and a method using a pressure nozzle. Any method can be used in the third step.
噴霧乾燥法において、霧化された液滴の大きさは特に限定されないが、1〜40μmが好ましく、5〜30μmが特に好ましい。噴霧乾燥装置へのスラリーの供給量は、この観点を考慮して決定することが望ましい。 In the spray drying method, the size of the atomized droplet is not particularly limited, but is preferably 1 to 40 μm, and particularly preferably 5 to 30 μm. It is desirable to determine the supply amount of the slurry to the spray dryer in consideration of this viewpoint.
なお、噴霧乾燥装置における熱風温度は、100〜270℃、好ましくは150〜230℃に調整することが粉体の吸湿を防ぎ粉体の回収が容易になることから好ましい。 The hot air temperature in the spray drying apparatus is preferably adjusted to 100 to 270 ° C., more preferably 150 to 230 ° C., because moisture absorption of the powder is prevented and the powder can be easily recovered.
<第2の方法>
以下、第2の方法で前記反応前駆体を製造する方法について説明する。
<Second method>
Hereinafter, a method for producing the reaction precursor by the second method will be described.
第2の方法に係る第A工程は、水酸化ジルコニウム及び炭酸ジルコニウムから選ばれるジルコニウム化合物、リン酸及びタングステン化合物を含むスラリーを加熱処理する工程である。 Step A according to the second method is a step of heat-treating a slurry containing a zirconium compound, phosphoric acid, and a tungsten compound selected from zirconium hydroxide and zirconium carbonate.
タングステン化合物を予め均一分散させたスラリーを調製した後に、リン酸及びジルコニウム化合物を添加しないと、タングステン化合物に起因してスラリーの粘性が高くなり、各原料を均一混合処理することが難しい傾向があるが、本発明者らは、タングステン化合物、リン酸及びジルコニウム化合物を含むスラリーを加熱処理することで、粘性が低くなり、メディアミルによる湿式粉砕処理が可能なスラリーが得られることを見出した。従って、第2の方法において、第A工程を施すことにより、リン酸とジルコニウム化合物との反応を行いつつ、タングステン化合物と、リンとジルコニウムを含む無定形の化合物が均一分散したスラリーを一気に得ることが出来る。 After preparing a slurry in which a tungsten compound is uniformly dispersed in advance, if the phosphoric acid and zirconium compound are not added, the viscosity of the slurry increases due to the tungsten compound, and it tends to be difficult to uniformly mix the raw materials. However, the present inventors have found that by subjecting a slurry containing a tungsten compound, phosphoric acid and a zirconium compound to heat treatment, a viscosity can be lowered and a slurry that can be wet pulverized by a media mill can be obtained. Therefore, in the second method, by carrying out the step A, a slurry in which the tungsten compound and the amorphous compound containing phosphorus and zirconium are uniformly dispersed can be obtained at once while the reaction between phosphoric acid and the zirconium compound is performed. I can do it.
第A工程に係るタングステン化合物、リン酸及びジルコニウム化合物は、前記第1の方法の第1工程及び第2工程と同じものを用いることが出来る。 As the tungsten compound, phosphoric acid and zirconium compound in the step A, the same compounds as those in the first step and the second step of the first method can be used.
ジルコニウム化合物のスラリーへの添加量は、スラリー中のタングステン化合物中のW元素に対するジルコニウム化合物中のZr元素のモル比(Zr/W)で1.7〜2.3、好ましくは1.9〜2.1とすることが負の熱膨張が大きなものが得られるという観点から好ましい。 The addition amount of the zirconium compound to the slurry is 1.7 to 2.3, preferably 1.9 to 2 in terms of the molar ratio (Zr / W) of the Zr element in the zirconium compound to the W element in the tungsten compound in the slurry. .1 is preferable from the viewpoint that a negative thermal expansion can be obtained.
リン酸のスラリーへの添加量は、スラリー中のタングステン化合物中のW元素に対するリン酸中のP元素のモル比(P/W)で1.7〜2.3、好ましくは1.9〜2.1とすることが負の熱膨張が大きなものが得られるという観点から好ましい。 The amount of phosphoric acid added to the slurry is 1.7 to 2.3, preferably 1.9 to 2, in terms of the molar ratio (P / W) of P element in phosphoric acid to W element in the tungsten compound in the slurry. .1 is preferable from the viewpoint that a negative thermal expansion can be obtained.
第A工程に係るタングステン化合物、リン酸及びジルコニウム化合物を分散させる溶媒は、水だけに限らず水と親水性溶媒との混合溶媒であってもよい。
第A工程に係るスラリー濃度は5〜50質量%、好ましくは10〜30質量%とすることが操作性と取扱いが容易な粘度のスラリーとなる観点から好ましい。
The solvent in which the tungsten compound, phosphoric acid, and zirconium compound in Step A are dispersed is not limited to water, and may be a mixed solvent of water and a hydrophilic solvent.
The slurry concentration in Step A is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass from the viewpoint of providing a slurry having a viscosity that is easy to handle and handle.
なお、第A工程において、各原料の添加順序は特に制限なく、反応装置等を考慮して行うことが好ましいが、タングステン化合物を含むスラリーを調製した後に、該スラリーにリン酸及びジルコニウム化合物を添加することが、より操作性が容易になると言う観点から好ましい。 In Step A, the order of addition of the respective raw materials is not particularly limited, and it is preferable to carry out in consideration of the reactor and the like. However, after preparing a slurry containing a tungsten compound, phosphoric acid and a zirconium compound are added to the slurry. It is preferable from the viewpoint that operability becomes easier.
第A工程のスラリー加熱処理温度は、40〜110℃、好ましくは60〜90℃とすることがリン酸とジルコニウム化合物との反応を行いつつ、操作性と取扱いが容易な粘度のスラリーとなる観点から好ましい。 The viewpoint that the slurry heat treatment temperature in the step A is 40 to 110 ° C., preferably 60 to 90 ° C., while the reaction between phosphoric acid and the zirconium compound is carried out, and the slurry becomes a slurry with easy handling and handling. To preferred.
第A工程での加熱処理時間は本製造方法において臨界的ではなく、リンとジルコニウムを含む無定形の化合物が生成し、またスラリー粘度が適度に下がるまで十分な時間反応を行えばよい。多くの場合、0.5時間以上、好ましくは1〜4時間で、満足の行く諸物性のタングステン化合物と、リンとジルコニウムを含む無定形の化合物が均一分散した粘性の低いスラリーを生成させることが出来る。 The heat treatment time in Step A is not critical in the present production method, and the reaction may be carried out for a sufficient time until an amorphous compound containing phosphorus and zirconium is formed and the slurry viscosity is appropriately lowered. In many cases, it is possible to produce a low-viscosity slurry in which a tungsten compound having satisfactory physical properties and an amorphous compound containing phosphorus and zirconium are uniformly dispersed in 0.5 hour or more, preferably 1 to 4 hours. I can do it.
次いで、第B工程で、第A工程で得られたスラリーをメディアミルで湿式粉砕処理する。 Next, in step B, the slurry obtained in step A is wet pulverized by a media mill.
第B工程は、第A工程後のスラリーをメディアミルで湿式粉砕処理して、微細で、且つ均一に各原料が分散されたスラリーを得る工程である。 The B step is a step in which the slurry after the A step is wet pulverized by a media mill to obtain a slurry in which each raw material is dispersed finely and uniformly.
メディアミルとしては、ビーズミル、ボールミル、ペイントシェーカー、アトライタ、サンドミル等を用いることができる。特にビーズミルを用いることが好ましい。その場合、運転条件やビーズの種類及び大きさは、装置のサイズや処理量に応じて適切に選択すればよい。 As the media mill, a bead mill, a ball mill, a paint shaker, an attritor, a sand mill, or the like can be used. It is particularly preferable to use a bead mill. In that case, the operating conditions and the type and size of the beads may be appropriately selected according to the size of the apparatus and the processing amount.
メディアミルを用いた処理を一層効率的に行う観点から、スラリーに、分散剤を加えてもよい。使用する分散剤は、分散媒の種類に応じて適切なものを選択すればよい。分散媒が例えば水である場合には、分散剤として各種の界面活性剤、ポリカルボン酸アンモニウム塩等を用いることができる。スラリーにおける分散剤の濃度は0.01〜10重量%、特に0.1〜5重量%とすることが、分散効果が高くなる観点で好ましい。 From the viewpoint of more efficiently performing the treatment using the media mill, a dispersant may be added to the slurry. What is necessary is just to select a suitable dispersing agent to use according to the kind of dispersion medium. When the dispersion medium is water, for example, various surfactants, polycarboxylic acid ammonium salts, and the like can be used as the dispersant. The concentration of the dispersant in the slurry is preferably 0.01 to 10% by weight, particularly 0.1 to 5% by weight from the viewpoint of increasing the dispersion effect.
メディアミルを用いた粉砕処理は、レーザー回折・散乱法により求められる固形分の平均粒子径が2μm以下、好ましくは1μm以下、特に好ましくは0.1〜0.5μmとなるまで行うと一層反応性に優れた反応前駆体を得ることができる観点から好ましい。 When the pulverization treatment using a media mill is carried out until the average particle size of the solid content determined by the laser diffraction / scattering method is 2 μm or less, preferably 1 μm or less, particularly preferably 0.1 to 0.5 μm, it becomes more reactive. It is preferable from the viewpoint that a reaction precursor excellent in the above can be obtained.
かくすることにより、微細なタングステン化合物と、リンとジルコニウムを含む無定形の化合物が均一分散した粘性の低いスラリーを調製することができる。 By doing so, a low-viscosity slurry in which a fine tungsten compound and an amorphous compound containing phosphorus and zirconium are uniformly dispersed can be prepared.
反応終了後、第B工程後のスラリーは固液分離せずに、第C工程で該スラリーを全量乾燥することで、第2の方法で本発明で使用する反応前駆体を得ることができる。スラリーを全量乾燥する方法として、特に制限されるものではないが、噴霧乾燥により乾燥処理を行うと原料粒子が密に詰まった状態の造粒物が得られることから、より一層X線回折的には単相のリン酸タングステン酸ジルコニウムが得やすくなる観点から好ましい。 After completion of the reaction, the reaction precursor used in the present invention in the second method can be obtained by drying the entire slurry in Step C without solid-liquid separation of the slurry after Step B. The method of drying the entire slurry is not particularly limited, but if a drying process is performed by spray drying, a granulated product in which raw material particles are densely packed is obtained. Is preferable from the viewpoint of easily obtaining single-phase zirconium tungstate phosphate.
噴霧乾燥法においては、所定手段によってスラリーを霧化し、それによって生じた微細な液滴を乾燥させることで反応前駆体を得る。スラリーの霧化には、例えば回転円盤を用いる方法と、圧力ノズルを用いる方法がある。第C工程においてはいずれの方法も用いることもできる。 In the spray-drying method, the reaction precursor is obtained by atomizing the slurry by a predetermined means and drying fine droplets generated thereby. The atomization of the slurry includes, for example, a method using a rotating disk and a method using a pressure nozzle. Any method can be used in Step C.
噴霧乾燥法において、霧化された液滴の大きさは特に限定されないが、1〜40μmが好ましく、5〜30μmが特に好ましい。噴霧乾燥装置へのスラリーの供給量は、この観点を考慮して決定することが望ましい。 In the spray drying method, the size of the atomized droplet is not particularly limited, but is preferably 1 to 40 μm, and particularly preferably 5 to 30 μm. It is desirable to determine the supply amount of the slurry to the spray dryer in consideration of this viewpoint.
なお、噴霧乾燥装置における熱風温度は、100〜270℃、好ましくは150〜230℃に調整することが粉体の吸湿を防ぎ粉体の回収が容易になることから好ましい。 The hot air temperature in the spray drying apparatus is preferably adjusted to 100 to 270 ° C., more preferably 150 to 230 ° C., because moisture absorption of the powder is prevented and the powder can be easily recovered.
本製造方法では、第1の方法及び第2の方法で得られる反応前駆体に焼結助剤成分を含有させることが出来る。 In this production method, a sintering aid component can be contained in the reaction precursor obtained by the first method and the second method.
焼結助剤成分としては、例えば、Mg、Zn、Cu、Fe、Cr、Mn、Ni、V、(Li、Al、B、Na、K、F、Cl、Br、I、Ca、Sr、Ba,Ti、Hf,Nb、Ta、Y、Yb、Si、S、Mo、Co、Bi、Te、Pb、Ag,Cd,In,Sn、Sb,Te,Ga、Ge、La、Ce、Nd、Sm、Eu、Tb、Dy及びHo等から選ばれる元素が挙げられ、これらは1種又は2種以上で用いることが出来る。これらの中、Mg及び/又はVから選ばれる元素が好ましい。 Examples of the sintering aid component include Mg, Zn, Cu, Fe, Cr, Mn, Ni, V, (Li, Al, B, Na, K, F, Cl, Br, I, Ca, Sr, Ba , Ti, Hf, Nb, Ta, Y, Yb, Si, S, Mo, Co, Bi, Te, Pb, Ag, Cd, In, Sn, Sb, Te, Ga, Ge, La, Ce, Nd, Sm , Eu, Tb, Dy, Ho, etc., can be used, and these can be used alone or in combination of two or more, among which elements selected from Mg and / or V are preferred.
前記焼結助剤成分は、該焼結助剤成分を含有する化合物として、第1の方法では、第二工程〜第三工程前のスラリーに、添加することが好ましい。
また、第2の方法では、第A工程〜第B工程前のスラリー、具体的には、第A工程を行う前、第A工程を行っている最中、第A工程の完了後、第B工程を行う前、及び第B工程を行っている最中のうちの少なくとも一つの場面において、該焼結助剤成分を含有する化合物を添加することが好ましい。
In the first method, the sintering aid component is preferably added as a compound containing the sintering aid component to the slurry before the second step to the third step.
In the second method, the slurry before Step A to Step B, specifically, before performing Step A, while performing Step A, after completion of Step A, after Step B, It is preferable to add a compound containing the sintering aid component before performing the step and in at least one scene during the step B.
焼結助剤成分を含有する化合物としては、前記焼結助剤成分を含む酸化物、水酸化物、炭酸塩、有機酸塩、アンモニウム塩、硝酸塩、リン酸塩、硫酸塩、塩化物、臭化物、ヨウ化物等が挙げられ、これらの中、焼結助剤成分を含む酸化物、水酸化物が製品の純度を制御しやすく、高純度品を得やすいという観点から好ましく用いられる。 The compound containing the sintering aid component includes oxides, hydroxides, carbonates, organic acid salts, ammonium salts, nitrates, phosphates, sulfates, chlorides, bromides containing the sintering aid components. Among these, oxides and hydroxides containing a sintering aid component are preferably used from the viewpoint of easily controlling the purity of the product and easily obtaining a high-purity product.
なお、第1の方法及び第2の方法では、添加した焼結助剤成分を含有する化合物がスラリー中に溶解もしくは析出するように、必要によりアルカリや酸でpHを調整することが出来る。 In the first method and the second method, if necessary, the pH can be adjusted with an alkali or an acid so that the compound containing the added sintering aid component is dissolved or precipitated in the slurry.
焼結助剤成分を含有する化合物のスラリーへの添加量は、得られる反応前駆体に焼結助剤成分として0.05〜5.0質量%、好ましくは0.1〜3.0質量%となるように添加することが好ましい。 The amount of the compound containing the sintering aid component added to the slurry is 0.05 to 5.0 mass%, preferably 0.1 to 3.0 mass% as the sintering aid component in the resulting reaction precursor. It is preferable to add so that it becomes.
焼結助剤成分は、反応前駆体中に、添加した焼結助剤成分を含有する化合物としてそのまま含有されていてもよく、添加した焼結助剤成分を含有する化合物がスラリー中で反応して他の焼結助剤成分を含有する化合物に転換して含有されていてもよい。
例えば、焼結助剤成分を含有する化合物として、水酸化物を用いた場合は、スラリー中でリン酸と反応し、焼結助剤成分を含有するリン酸塩に転換して反応前駆体中に含有される場合がある。
なお、反応前駆体中に含有される焼結助剤成分を含有する化合物は結晶質或いは不定形のものであってもよい。
The sintering aid component may be directly contained in the reaction precursor as a compound containing the added sintering aid component, and the compound containing the added sintering aid component reacts in the slurry. It may be converted into a compound containing another sintering aid component.
For example, when a hydroxide is used as the compound containing the sintering aid component, it reacts with phosphoric acid in the slurry, and is converted into a phosphate containing the sintering aid component, in the reaction precursor. May be contained.
The compound containing the sintering aid component contained in the reaction precursor may be crystalline or amorphous.
本発明では、前記反応前駆体を焼成する焼成工程を設けることにより目的とするリン酸タングステン酸ジルコニウムを得ることが出来る。 In the present invention, the target zirconium phosphate tungstate can be obtained by providing a firing step for firing the reaction precursor.
焼成工程において、反応前駆体を焼成する焼成温度は900〜1300℃である。この理由は焼成温度が900℃未満では未反応の酸化物等が残存しX線回折的に単相のリン酸タングステン酸ジルコニウムを得ることが難しくなる傾向があり、一方、焼成温度が1300℃より高くなると粒子同士が固結した状態の塊になり粉末が得られにくい傾向があるからである。
なお、本製造方法では、低温でX線回折的に単相のリン酸タングステン酸ジルコニウムを得ることが可能なので、この利点を生かすため焼成温度を900〜1100℃として行うことが好ましい。
In the firing step, the firing temperature for firing the reaction precursor is 900 to 1300 ° C. The reason for this is that when the firing temperature is less than 900 ° C., unreacted oxides or the like remain and it becomes difficult to obtain single-phase zirconium tungstate phosphate by X-ray diffraction, while the firing temperature is more than 1300 ° C. This is because when the particle size is high, the particles tend to be consolidated into a lump and it is difficult to obtain a powder.
In this production method, it is possible to obtain single-phase zirconium tungstate phosphate by X-ray diffraction at a low temperature. Therefore, it is preferable to perform the firing temperature at 900 to 1100 ° C. in order to take advantage of this advantage.
焼成時間は、本製造方法において臨界的ではなく、X線回折的に単相のリン酸タングステン酸ジルコニウムが生成するまで十分な時間反応を行う。多くの場合、1時間以上、好ましくは2〜20時間で、満足の行く諸物性のリン酸タングステン酸ジルコニウムを生成させることが出来る。また、焼成雰囲気は、特に制限されず、不活性ガス雰囲気下、真空雰囲気下、酸化性ガス雰囲気下、大気中のいずれであってもよい。 The firing time is not critical in the present production method, and the reaction is carried out for a sufficient time until single-phase zirconium tungstate phosphate is produced by X-ray diffraction. In many cases, satisfactory zirconium phosphate tungstate can be produced in 1 hour or longer, preferably 2 to 20 hours. The firing atmosphere is not particularly limited, and may be any of an inert gas atmosphere, a vacuum atmosphere, an oxidizing gas atmosphere, and the air.
焼成は所望により何度行ってもよい。或いは、粉体特性を均一にする目的で、一度焼成したものを粉砕し、次いで再焼成を行ってもよい。 Firing may be performed as many times as desired. Alternatively, for the purpose of making the powder characteristics uniform, the fired material may be pulverized and then refired.
焼成後、適宜冷却し、必要に応じ粉砕、解砕、分級等を行って目的とするX線回折的に単相のリン酸タングステン酸ジルコニウムを得ることができる。 After firing, the product is cooled as appropriate, and pulverized, crushed, classified, etc., as necessary, to obtain the target X-ray diffraction single phase zirconium phosphate tungstate.
本製造方法で得られるリン酸タングステン酸ジルコニウムは、Zr2(WO4)(PO4)2で表され、X線回折的に単相のリン酸タングステン酸ジルコニウムであることに加えて、走査型電子顕微鏡観察により求められる平均一次粒子径が5μm以下、好ましくは0.1〜4μm、平均二次粒子径が1〜40μm、好ましくは4〜30μmであり、BET比表面積は0.1〜20m2/g、好ましくは0.1〜10m2/gであることが、該リン酸タングステン酸ジルコニウムを樹脂やガラス等へのフィラー用として用いる際に、取り扱いが容易になる観点から好ましい。 Zirconium tungstate phosphate obtained by this production method is represented by Zr 2 (WO 4 ) (PO 4 ) 2 , and in addition to being X-ray diffraction single phase zirconium tungstate phosphate, a scanning type The average primary particle diameter determined by electron microscope observation is 5 μm or less, preferably 0.1 to 4 μm, the average secondary particle diameter is 1 to 40 μm, preferably 4 to 30 μm, and the BET specific surface area is 0.1 to 20 m 2. / g, preferably 0.1 to 10 m 2 / g, is preferred from the viewpoint of easy handling when the zirconium phosphate tungstate is used as a filler for resin, glass or the like.
本製造方法で得られるリン酸タングステン酸ジルコニウムは、特に負の熱膨張を示す負熱膨張材として有用であり、本製造方法で得られるリン酸タングステン酸ジルコニウムは0〜400℃の温度範囲における線膨張係数は−3.4〜−2.6ppm/℃、好ましくは−3.4〜−2.8ppm/℃である。 Zirconium tungstate phosphate obtained by this production method is particularly useful as a negative thermal expansion material exhibiting negative thermal expansion. Zirconium tungstate phosphate obtained by this production method is a wire in a temperature range of 0 to 400 ° C. The expansion coefficient is -3.4 to -2.6 ppm / ° C, preferably -3.4 to -2.8 ppm / ° C.
本製造方法で得られるリン酸タングステン酸ジルコニウムは、粉体又はペーストとして用いることが出来る。ペーストとして用いる場合には、粘性の低い液状樹脂とのペーストの状態で用いることができる。あるいは、溶解、更に必要によりバインダー、フラックス材及び分散剤等を含有させたペーストの状態で用いても良い。 Zirconium tungstate phosphate obtained by this production method can be used as a powder or a paste. When used as a paste, it can be used in the state of a paste with a liquid resin having a low viscosity. Or you may use in the state of the paste which melt | dissolved and also contained the binder, the flux material, the dispersing agent, etc. as needed.
本製造方法で得られるリン酸タングステン酸ジルコニウムは各種有機化合物または無機化合物と併用して複合材料として用いることが出来る。上記有機化合物または無機化合物は特に限定されないが、有機化合物としては、ゴム、ポリオレフィン、ポリシクロオレフィン、ポリスチレン、ABS、ポリアクリレート、ポリフェニレンスルファイド、フェノール樹脂、ポリアミド樹脂、ポリイミド樹脂、エポキシ樹脂、シリコーン樹脂、ポリカーボネート樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリエチレンテレフタラート樹脂(PET樹脂)およびポリ塩化ビニル樹脂などを挙げることができる。また、無機化合物としては、二酸化ケイ素、グラファイト、サファイア、各種のガラス材料、コンクリート材料、各種のセラミック材料などを挙げることができる。 Zirconium tungstate phosphate obtained by this production method can be used as a composite material in combination with various organic compounds or inorganic compounds. The organic compound or the inorganic compound is not particularly limited. Examples of the organic compound include rubber, polyolefin, polycycloolefin, polystyrene, ABS, polyacrylate, polyphenylene sulfide, phenol resin, polyamide resin, polyimide resin, epoxy resin, and silicone resin. , Polycarbonate resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin (PET resin), and polyvinyl chloride resin. Examples of inorganic compounds include silicon dioxide, graphite, sapphire, various glass materials, concrete materials, and various ceramic materials.
上記複合材料は、本発明に係る負熱膨張材となるリン酸タングステン酸ジルコニウムを含んでいるため、他の化合物との配合比率によって、負熱膨張率、零熱膨張率または低熱膨張率を実現することが可能である。 Since the above composite material contains zirconium tungstate phosphate, which is the negative thermal expansion material according to the present invention, a negative thermal expansion coefficient, a zero thermal expansion coefficient, or a low thermal expansion coefficient is realized depending on the blending ratio with other compounds. Is possible.
以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。
<評価装置>
1.X線回折分析:リン酸タングステン酸ジルコニウムと反応前駆体のX線回折分析は、リガク社 UltimaIVを用いた。線源としてCu−Kαを用いた。測定条件は、管電圧40kV、管電流40mA、走査速度0.1°/secとした。
2.赤外吸収スペクトル(FT−IR)分析:反応前駆体の赤外吸収スペクトル分析は、サーモフィッシャーサイエンティフィック社製NICOLET6700により、分解能:4cm-1、積算数:256回、測定波数領域:400cm-1〜4000cm-1の条件にて測定した。ATR法により測定し、ATR補正及びスペクトルのスムージング処理を行った。
3.平均粒子径;各原料及びスラリー中の固形分の平均粒子径はレーザー回折・散乱法により、マイクロトラックMT3300EXII粒度分析計(マイクロトラック・ベル社製)を用いて測定した。
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
<Evaluation equipment>
1. X-ray diffraction analysis: Rigaku Ultima IV was used for X-ray diffraction analysis of zirconium phosphate tungstate and the reaction precursor. Cu-Kα was used as the radiation source. The measurement conditions were a tube voltage of 40 kV, a tube current of 40 mA, and a scanning speed of 0.1 ° / sec.
2. Infrared absorption spectrum (FT-IR) analysis: Infrared absorption spectrum analysis of the reaction precursor was performed using a NICOLET 6700 manufactured by Thermo Fisher Scientific, resolution: 4 cm −1 , integration number: 256 times, measurement wave number region: 400 cm −. Measurement was performed under conditions of 1 to 4000 cm −1 . Measurement was performed by the ATR method, and ATR correction and spectrum smoothing were performed.
3. Average particle diameter: The average particle diameter of the solid content in each raw material and slurry was measured by a laser diffraction / scattering method using a Microtrac MT3300EXII particle size analyzer (manufactured by Microtrac Bell).
{実施例1}
市販の三酸化タングステン(WO3;平均粒子径1.2μm)15質量部をビーカーに入れ、更に純水84重量部を添加し、分散剤としてポリカルボン酸アンモニウム塩を1重量部、仕込んだ。
室温(25℃)でスリーワンモーター攪拌機を用いて120分間撹拌して、三酸化タングステンを含む15質量%スラリーを調製した。スラリー中の固形分の平均粒子径は1.2μmであった。
次いで、このスラリーに水酸化ジルコニウムと、85質量%リン酸水溶液とを、スラリー中のZr:W:Pのモル比が2.00:1.00:2.00となるように室温(25℃)で添加し、2時間撹拌下に反応を行った。
反応終了後、スラリーの全量を200℃で大気下に24時間乾燥を行って、反応前駆体を得た。得られた反応前駆体についてX線回折を行った結果、三酸化タングステンの回折ピークのみが観察された(図1参照)。また、FT−IRで分析を行ったところ、950〜1150cm-1に赤外線吸収ピークを持ち、この間の赤外線吸収ピークの極大値は1027cm-1に現れた(図2参照)。
次いで、得られた反応前駆体を950℃で2時間大気中で焼成反応を行い、白色の焼成品を得た。
得られた焼成品をX線回折分析したところ、焼成品は単相のZr2(WO4)(PO4)2であった(図3参照)。
{Example 1}
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 μm) was placed in a beaker, 84 parts by weight of pure water was further added, and 1 part by weight of polycarboxylic acid ammonium salt was charged as a dispersant.
The mixture was stirred for 120 minutes using a three-one motor stirrer at room temperature (25 ° C.) to prepare a 15 mass% slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 μm.
Subsequently, zirconium hydroxide and 85 mass% phosphoric acid aqueous solution were added to this slurry at room temperature (25 ° C. so that the molar ratio of Zr: W: P in the slurry was 2.00: 1.00: 2.00. The reaction was carried out with stirring for 2 hours.
After completion of the reaction, the entire amount of the slurry was dried at 200 ° C. in the atmosphere for 24 hours to obtain a reaction precursor. As a result of performing X-ray diffraction on the obtained reaction precursor, only the diffraction peak of tungsten trioxide was observed (see FIG. 1 ). When it was analyzed by FT-IR, has an infrared absorption peak at 950~1150Cm -1, the maximum value of this period of the infrared absorption peak appeared at 1027cm -1 (see FIG. 2).
Next, the obtained reaction precursor was subjected to a calcination reaction at 950 ° C. for 2 hours in the air to obtain a white baked product.
When the obtained fired product was analyzed by X-ray diffraction, the fired product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 (see FIG. 3).
{実施例2}
市販の三酸化タングステン(WO3;平均粒子径25μm)15質量部を秤量しタンクに仕込んだ。タンクに純水84重量部、分散剤としてポリカルボン酸アンモニウム塩を1重量部、仕込んだ。
次いで、スラリーを攪拌しながら、直径0.5mmのジルコニアビーズを仕込んだメディア攪拌型ビーズミルに供給し、15分間混合して湿式粉砕を行った。湿式粉砕後のスラリー中の固形分の平均粒子径は0.3μmであった。
次いで、このスラリーに水酸化ジルコニウムと、85質量%リン酸水溶液とを、スラリー中のZr:W:Pのモル比が2.00:1.00:2.00となるように室温(25℃)で添加し、2時間撹拌下に反応を行った。
反応終了後、220℃に設定したスプレードライヤーに、2.4L/hの供給速度でスラリーを供給し、反応前駆体を得た。得られた反応前駆体について、X線回折を行った結果、三酸化タングステンの回折ピークのみが観察された。また、FT−IRで分析を行ったところ、950〜1150cm-1に赤外線吸収ピークを持ち、この間の赤外線吸収ピークの極大値は1030cm-1に現れた。
次いで、得られた反応前駆体を950℃で2時間大気中、焼成反応を行い、白色の焼成品を得た。
得られた焼成品をX線回折分析したところ、焼成品は単相のZr2(WO4)(PO4)2であった。
{Example 2}
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 25 μm) was weighed and charged into a tank. The tank was charged with 84 parts by weight of pure water and 1 part by weight of polycarboxylic acid ammonium salt as a dispersant.
Next, while stirring the slurry, the slurry was supplied to a media stirring type bead mill charged with zirconia beads having a diameter of 0.5 mm, mixed for 15 minutes, and wet pulverized. The average particle size of the solid content in the slurry after the wet pulverization was 0.3 μm.
Subsequently, zirconium hydroxide and 85 mass% phosphoric acid aqueous solution were added to this slurry at room temperature (25 ° C. so that the molar ratio of Zr: W: P in the slurry was 2.00: 1.00: 2.00. The reaction was carried out with stirring for 2 hours.
After completion of the reaction, the slurry was supplied to a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor. As a result of performing X-ray diffraction on the obtained reaction precursor, only the diffraction peak of tungsten trioxide was observed. In addition, was subjected to analysis by FT-IR, has an infrared absorption peak in 950~1150cm -1, the maximum value of this period of the infrared absorption peak appeared at 1030cm -1.
Subsequently, the obtained reaction precursor was subjected to a calcination reaction at 950 ° C. for 2 hours in the air to obtain a white baked product.
As a result of X-ray diffraction analysis of the obtained fired product, the fired product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 .
{比較例1}
市販の三酸化タングステン(WO3;平均粒子径25μm)7質量部と市販の酸化ジルコニウム(ZrO2;平均粒子径6.5μm)とを秤量しW:Zrのモル比が2.00:1.00となるようにタンクに仕込んだ。タンクに純水84重量部、分散剤としてポリカルボン酸アンモニウム塩を1重量部を加え、固形分濃度が15%のスラリーを調製した。
次いで、スラリーを攪拌しながら、直径0.5mmのジルコニアビーズを仕込んだメディア攪拌型ビーズミルに供給し、15分間混合して湿式粉砕を行った。湿式粉砕後のスラリー中の固形分の平均粒子径は0.3μmであった。
次いで、このスラリーに85質量%リン酸水溶液を、スラリー中のZr:W:Pのモル比が2.00:1.00:2.00となるように添加し、室温(25℃)で2時間撹拌を行った。
反応終了後、スラリーの全量を200℃で大気下に24時間乾燥を行って、反応前駆体を得た。得られた反応前駆体についてX線回折を行った結果、三酸化タングステンと酸化ジルコニウムの回折ピークが観察された(図4参照)。
次いで、得られた反応前駆体を950℃で2時間大気中で焼成反応を行い、緑白色の焼成品を得た。
得られた焼成品をX線回折分析したところ、焼成品は異相を多く含むものでZr2(WO4)(PO4)2の生成は僅かであった(図5参照)。
{Comparative Example 1}
7 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter 25 μm) and commercially available zirconium oxide (ZrO 2 ; average particle diameter 6.5 μm) were weighed, and the molar ratio of W: Zr was 2.00: 1. The tank was charged to 00. 84 parts by weight of pure water and 1 part by weight of polycarboxylic acid ammonium salt as a dispersant were added to the tank to prepare a slurry having a solid content of 15%.
Next, while stirring the slurry, the slurry was supplied to a media stirring type bead mill charged with zirconia beads having a diameter of 0.5 mm, mixed for 15 minutes, and wet pulverized. The average particle size of the solid content in the slurry after the wet pulverization was 0.3 μm.
Subsequently, 85 mass% phosphoric acid aqueous solution was added to this slurry so that the molar ratio of Zr: W: P in the slurry would be 2.00: 1.00: 2.00, and 2 at room temperature (25 ° C.). Stir for hours.
After completion of the reaction, the entire amount of the slurry was dried at 200 ° C. in the atmosphere for 24 hours to obtain a reaction precursor. As a result of performing X-ray diffraction on the obtained reaction precursor, diffraction peaks of tungsten trioxide and zirconium oxide were observed (see FIG. 4).
Next, the obtained reaction precursor was subjected to a calcination reaction at 950 ° C. for 2 hours in the air to obtain a greenish white baked product.
When the obtained fired product was analyzed by X-ray diffraction, it was found that the fired product contained a large amount of different phases, and Zr 2 (WO 4 ) (PO 4 ) 2 was little produced (see FIG. 5).
<物性評価>
実施例1〜2及び比較例1で得られたリン酸タングステン酸ジルコニウムについて、平均一次粒子径、平均二次粒子径、BET比表面積及び熱膨張係数を測定した。その結果を表1に示す。また、実施例2で得られたリン酸タングステン酸ジルコニウムのSEM写真を図6に示す。
<Physical property evaluation>
About the zirconium tungstate phosphate obtained in Examples 1 and 2 and Comparative Example 1, the average primary particle diameter, the average secondary particle diameter, the BET specific surface area, and the thermal expansion coefficient were measured. The results are shown in Table 1. Moreover, the SEM photograph of the zirconium tungstate phosphate obtained in Example 2 is shown in FIG.
(平均一次粒子径の評価)
リン酸タングステン酸ジルコニウムの平均一次粒子径は、走査型電子顕微鏡観察において倍率5千倍で任意に抽出した粒子50個以上の平均値により求めた。
(平均二次粒子径の評価)
リン酸タングステン酸ジルコニウムの平均二次粒子径は、走査型電子顕微鏡観察において倍率400倍で任意に抽出した粒子50個以上の平均値により求めた。
(線膨張係数の評価)
昇温機能が付いたXRD装置(リガク社 UltimaIV)にて、昇温速度20℃/minで、目標温度に到達してから10分後に試料のa軸、b軸、c軸に対する格子定数を測定し、格子体積変化(直方体)を線換算して線膨張係数を求めた(J. Mat. Sci.,35(2000)2451−2454参照)。
(Evaluation of average primary particle size)
The average primary particle diameter of zirconium phosphate tungstate was determined by an average value of 50 or more particles arbitrarily extracted at a magnification of 5,000 times in a scanning electron microscope.
(Evaluation of average secondary particle size)
The average secondary particle diameter of zirconium phosphate tungstate was determined by an average value of 50 or more particles arbitrarily extracted at a magnification of 400 times in a scanning electron microscope.
(Evaluation of linear expansion coefficient)
Lattice constants for the a-axis, b-axis, and c-axis of the sample are measured 10 minutes after reaching the target temperature at a temperature increase rate of 20 ° C / min using an XRD device with a temperature increase function (Rigaku Ultima IV). Then, a linear expansion coefficient was obtained by converting the lattice volume change (cuboid) into a line (see J. Mat. Sci., 35 (2000) 2451-2454).
{実施例3}
市販の三酸化タングステン(WO3;平均粒子径1.2μm)15質量部をビーカーに入れ、更に純水84重量部を添加した。
室温(25℃)で120分間撹拌して、三酸化タングステンを含む15質量%スラリーを調製した。スラリー中の固形分の平均粒子径は1.2μmであった。
次いで、このスラリーに水酸化ジルコニウムと、85質量%リン酸水溶液と水酸化マグネシウムとを、スラリー中のZr:W:P:Mgのモル比が2.00:1.00:2.00:0.1となるように室温(25℃)で添加した後、80℃に昇温して4時間撹拌下に反応を行った。
反応終了後、分散剤としてポリカルボン酸アンモニウム塩を1重量部、仕込み、スラリーを攪拌しながら、直径0.5mmのジルコニアビーズを仕込んだメディア攪拌型ビーズミルに供給し、15分間混合して湿式粉砕を行った。湿式粉砕後のスラリー中の固形分の平均粒子径は0.3μmであった。
次いで、220℃に設定したスプレードライヤーに、2.4L/hの供給速度でスラリーを供給し、反応前駆体を得た。得られた反応前駆体について、X線回折を行った結果、三酸化タングステンの回折ピークのみが観察された(図7参照)。また、FT−IRで分析を行ったところ、950〜1150cm−1に赤外線吸収ピークを持ち、この間の赤外線吸収ピークの極大値は1042cm−1に現れた(図8参照)。
なお、焼結助剤成分のMgは、スラリー中でのリン酸と水酸化マグネシウムとの反応により、反応前駆体中で不定形のリン酸マグネシウムとして存在しているものと推測される。
次いで、得られた反応前駆体を1050℃で2時間大気中で焼成反応を行い、白色の焼成品を得た。
得られた焼成品をX線回折分析したところ、焼成品は単相のZr2(WO4)(PO4)2であった(図9参照)。
{Example 3}
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 μm) was placed in a beaker, and 84 parts by weight of pure water was further added.
The mixture was stirred at room temperature (25 ° C.) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 μm.
Next, zirconium hydroxide, 85 mass% phosphoric acid aqueous solution and magnesium hydroxide are added to this slurry, and the molar ratio of Zr: W: P: Mg in the slurry is 2.00: 1.00: 2.00: 0. .1 was added at room temperature (25 ° C.), and the mixture was heated to 80 ° C. and reacted with stirring for 4 hours.
After completion of the reaction, 1 part by weight of polycarboxylic acid ammonium salt was added as a dispersant, and the slurry was agitated and supplied to a media agitation type bead mill charged with zirconia beads having a diameter of 0.5 mm. Went. The average particle size of the solid content in the slurry after the wet pulverization was 0.3 μm.
Next, the slurry was supplied to a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor. As a result of performing X-ray diffraction on the obtained reaction precursor, only the diffraction peak of tungsten trioxide was observed (see FIG. 7). When it was analyzed by FT-IR, has an infrared absorption peak at 950~1150Cm -1, the maximum value of this period of the infrared absorption peak appeared at 1042cm -1 (see FIG. 8).
In addition, it is estimated that Mg of the sintering aid component exists as amorphous magnesium phosphate in the reaction precursor due to a reaction between phosphoric acid and magnesium hydroxide in the slurry.
Next, the obtained reaction precursor was subjected to a calcination reaction at 1050 ° C. for 2 hours in the air to obtain a white baked product.
The obtained fired product was analyzed by X-ray diffraction. As a result, the fired product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 (see FIG. 9).
{実施例4}
市販の三酸化タングステン(WO3;平均粒子径1.2μm)15質量部をビーカーに入れ、更に純水84重量部を添加し、分散剤としてポリカルボン酸アンモニウム塩を1重量部、仕込んだ。
室温(25℃)で120分間撹拌して、三酸化タングステンを含む15質量%スラリーを調製した。スラリー中の固形分の平均粒子径は1.2μmであった。
次いで、このスラリーに水酸化ジルコニウムと、85質量%リン酸水溶液と水酸化マグネシウムと五酸化二バナジウムとを、スラリー中のZr:W:P:Mg:Vのモル比が2.00:1.00:2.00:0.1:0.05となるように室温(25℃)で添加した後、80℃に昇温して4時間撹拌下に反応を行った。
反応終了後、スラリーを攪拌しながら、直径0.5mmのジルコニアビーズを仕込んだメディア攪拌型ビーズミルに供給し、15分間混合して湿式粉砕を行った。湿式粉砕後のスラリー中の固形分の平均粒子径は0.3μmであった。
次いで、220℃に設定したスプレードライヤーに、2.4L/hの供給速度でスラリーを供給し、反応前駆体を得た。得られた反応前駆体について、X線回折を行った結果、三酸化タングステンの回折ピークのみが観察された。また、FT−IRで分析を行ったところ、950〜1150cm−1に赤外線吸収ピークを持ち、この間の赤外線吸収ピークの極大値は1030cm−1に現れた。
なお、焼結助剤成分のMgは、スラリー中でのリン酸と水酸化マグネシウムとの反応により、反応前駆体中で不定形のリン酸マグネシウムとして存在しているものと推測される。一方、焼結助剤成分のVは、X線回折では、検出限界以下であるため回折ピークは検出されなかったが、五酸化二バナジウムとして反応前駆体中に存在しているものと推測される。
次いで、得られた反応前駆体を1050℃で2時間大気中で焼成反応を行い、白色の焼成品を得た。
得られた焼成品をX線回折分析したところ、焼成品は単相のZr2(WO4)(PO4)2であった。
{Example 4}
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 μm) was placed in a beaker, 84 parts by weight of pure water was further added, and 1 part by weight of polycarboxylic acid ammonium salt was charged as a dispersant.
The mixture was stirred at room temperature (25 ° C.) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 μm.
Next, zirconium hydroxide, 85 mass% phosphoric acid aqueous solution, magnesium hydroxide, and divanadium pentoxide were added to this slurry, and the molar ratio of Zr: W: P: Mg: V in the slurry was 2.00: 1. After adding at room temperature (25 ° C.) so as to be 00: 2.00: 0.1: 0.05, the temperature was raised to 80 ° C. and the reaction was carried out with stirring for 4 hours.
After completion of the reaction, while stirring the slurry, the slurry was supplied to a media stirring type bead mill charged with zirconia beads having a diameter of 0.5 mm, mixed for 15 minutes, and wet pulverized. The average particle size of the solid content in the slurry after the wet pulverization was 0.3 μm.
Next, the slurry was supplied to a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor. As a result of performing X-ray diffraction on the obtained reaction precursor, only the diffraction peak of tungsten trioxide was observed. In addition, was subjected to analysis by FT-IR, has an infrared absorption peak in 950~1150cm -1, the maximum value of this period of the infrared absorption peak appeared at 1030cm -1.
In addition, it is estimated that Mg of the sintering aid component exists as amorphous magnesium phosphate in the reaction precursor due to a reaction between phosphoric acid and magnesium hydroxide in the slurry. On the other hand, since V of the sintering aid component is below the detection limit in X-ray diffraction, a diffraction peak was not detected, but it is presumed to exist in the reaction precursor as divanadium pentoxide. .
Next, the obtained reaction precursor was subjected to a calcination reaction at 1050 ° C. for 2 hours in the air to obtain a white baked product.
When the obtained baked product was analyzed by X-ray diffraction, the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 .
{実施例5}
市販の三酸化タングステン(WO3;平均粒子径1.2μm)15質量部をビーカーに入れ、更に純水84重量部を添加した。
室温(25℃)で120分間撹拌して、三酸化タングステンを含む15質量%スラリーを調製した。スラリー中の固形分の平均粒子径は1.2μmであった。
次いで、このスラリーに水酸化ジルコニウムと、85質量%リン酸水溶液と水酸化マグネシウムとを、スラリー中のZr:W:P:Mgのモル比が2.00:1.00:2.00:0.1となるように室温(25℃)で添加した後、80℃に昇温して4時間撹拌下に反応を行った。
反応終了後、分散剤としてポリカルボン酸アンモニウム塩を1重量部、仕込み、スラリーを攪拌しながら、直径0.5mmのジルコニアビーズを仕込んだメディア攪拌型ビーズミルに供給し、15分間混合して湿式粉砕を行った。湿式粉砕後のスラリー中の固形分の平均粒子径は0.3μmであった。
次いで、220℃に設定したスプレードライヤーに、2.4L/hの供給速度でスラリーを供給し、反応前駆体を得た。得られた反応前駆体について、X線回折を行った結果、三酸化タングステンの回折ピークのみが観察された。また、FT−IRで分析を行ったところ、950〜1150cm−1に赤外線吸収ピークを持ち、この間の赤外線吸収ピークの極大値は1030cm−1に現れた。
なお、焼結助剤成分のMgは、スラリー中でのリン酸と水酸化マグネシウムとの反応により、反応前駆体中で不定形のリン酸マグネシウムとして存在しているものと推測される。
次いで、得られた反応前駆体を960℃で2時間大気中で焼成反応を行い、白色の焼成品を得た。これを気流式粉砕機で粉砕して粉砕品を得た。
得られた焼成品をX線回折分析したところ、焼成品は単相のZr2(WO4)(PO4)2であった。
{Example 5}
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 μm) was placed in a beaker, and 84 parts by weight of pure water was further added.
The mixture was stirred at room temperature (25 ° C.) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 μm.
Next, zirconium hydroxide, 85 mass% phosphoric acid aqueous solution and magnesium hydroxide are added to this slurry, and the molar ratio of Zr: W: P: Mg in the slurry is 2.00: 1.00: 2.00: 0. .1 was added at room temperature (25 ° C.), and the mixture was heated to 80 ° C. and reacted with stirring for 4 hours.
After completion of the reaction, 1 part by weight of polycarboxylic acid ammonium salt was added as a dispersant, and the slurry was agitated and supplied to a media agitation type bead mill charged with zirconia beads having a diameter of 0.5 mm. Went. The average particle size of the solid content in the slurry after the wet pulverization was 0.3 μm.
Next, the slurry was supplied to a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor. As a result of performing X-ray diffraction on the obtained reaction precursor, only the diffraction peak of tungsten trioxide was observed. In addition, was subjected to analysis by FT-IR, has an infrared absorption peak in 950~1150cm -1, the maximum value of this period of the infrared absorption peak appeared at 1030cm -1.
In addition, it is estimated that Mg of the sintering aid component exists as amorphous magnesium phosphate in the reaction precursor due to a reaction between phosphoric acid and magnesium hydroxide in the slurry.
Next, the obtained reaction precursor was subjected to a calcination reaction at 960 ° C. for 2 hours in the air to obtain a white baked product. This was pulverized with an airflow pulverizer to obtain a pulverized product.
When the obtained baked product was analyzed by X-ray diffraction, the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 .
{実施例6}
市販の三酸化タングステン(WO3;平均粒子径1.2μm)15質量部をビーカーに入れ、更に純水84質量部を添加した。
室温(25℃)で120分間撹拌して、三酸化タングステンを含む15質量%スラリーを調製した。スラリー中の固形分の平均粒子径は1.2μmであった。
次いで、このスラリーに水酸化ジルコニウムと、85質量%リン酸水溶液とを、スラリー中のZr:W:Pのモル比が2.00:1.00:2.00となるように室温(25℃)で添加した後、80℃に昇温して4時間撹拌下に反応を行った。
反応終了後、分散剤としてポリカルボン酸アンモニウム塩を1質量部、仕込み、スラリーを撹拌しながら、直径0.5mmのジルコニアビーズを仕込んだメディア撹拌型ビーズミルに供給し、15分間混合して湿式粉砕を行った。湿式粉砕後のスラリー中の固形分の平均粒子径は0.3μmであった。
次いで、220℃に設定したスプレードライヤーに、2.4L/hの供給速度でスラリーを供給し、反応前駆体を得た。得られた反応前駆体について、X線回折を行った結果、三酸化タングステンの回折ピークのみが観察された。また、FT−IRで分析を行ったところ、950〜1150cm−1に赤外線吸収ピークを持ち、この間の赤外線吸収ピークの極大値は1042cm−1に現れた。
次いで、得られた反応前駆体を1220℃で8時間にわたり大気中で焼成反応を行い、白色の焼成品を得た。
得られた焼成品をX線回折分析したところ、焼成品は単相のZr2(WO4)(PO4)2であった。
{Example 6}
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle size 1.2 μm) was placed in a beaker, and 84 parts by mass of pure water was further added.
The mixture was stirred at room temperature (25 ° C.) for 120 minutes to prepare a 15% by mass slurry containing tungsten trioxide. The average particle size of the solid content in the slurry was 1.2 μm.
Subsequently, zirconium hydroxide and 85 mass% phosphoric acid aqueous solution were added to this slurry at room temperature (25 ° C. so that the molar ratio of Zr: W: P in the slurry was 2.00: 1.00: 2.00. Then, the temperature was raised to 80 ° C. and the reaction was carried out with stirring for 4 hours.
After completion of the reaction, 1 part by weight of polycarboxylic acid ammonium salt as a dispersing agent is charged, and while stirring the slurry, it is supplied to a media stirring type bead mill charged with 0.5 mm diameter zirconia beads, mixed for 15 minutes and wet pulverized Went. The average particle size of the solid content in the slurry after the wet pulverization was 0.3 μm.
Next, the slurry was supplied to a spray dryer set at 220 ° C. at a supply rate of 2.4 L / h to obtain a reaction precursor. As a result of performing X-ray diffraction on the obtained reaction precursor, only the diffraction peak of tungsten trioxide was observed. In addition, was subjected to analysis by FT-IR, has an infrared absorption peak in 950~1150cm -1, the maximum value of this period of the infrared absorption peak appeared at 1042cm -1.
Next, the obtained reaction precursor was subjected to a calcination reaction in the air at 1220 ° C. for 8 hours to obtain a white baked product.
When the obtained baked product was analyzed by X-ray diffraction, the baked product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 .
<物性評価>
実施例3〜6で得られたリン酸タングステン酸ジルコニウムについて、実施例1〜2及び比較例1と同様にして平均一次粒子径、平均二次粒子径、BET比表面積及び線熱膨張係数を測定した。その結果を表2に示す。また、実施例3で得られたリン酸タングステン酸ジルコニウムのSEM写真を図10(上;30000倍、下;400倍)に示す。
<Physical property evaluation>
For the zirconium phosphate tungstate obtained in Examples 3 to 6, the average primary particle diameter, average secondary particle diameter, BET specific surface area and linear thermal expansion coefficient were measured in the same manner as in Examples 1 and 2 and Comparative Example 1. did. The results are shown in Table 2. Moreover, the SEM photograph of the zirconium phosphate tungstate obtained in Example 3 is shown in FIG. 10 (upper: 30000 times, lower: 400 times).
Claims (15)
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CN201680055927.2A CN108137325B (en) | 2015-10-07 | 2016-10-04 | Method for preparing zirconium phosphotungstate |
US15/763,627 US10167197B2 (en) | 2015-10-07 | 2016-10-04 | Method for producing zirconium tungsten phosphate |
PCT/JP2016/079396 WO2017061402A1 (en) | 2015-10-07 | 2016-10-04 | Production method for zirconium tungsten phosphate |
KR1020187008500A KR102611412B1 (en) | 2015-10-07 | 2016-10-04 | Method for producing zirconium tungstate phosphate |
TW105132119A TWI750137B (en) | 2015-10-07 | 2016-10-05 | Method for manufacturing zirconium tungstate phosphate |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002517377A (en) * | 1998-05-19 | 2002-06-18 | コーニング インコーポレイテッド | Negative intumescent material, method for its preparation and use |
JP2005035840A (en) * | 2003-07-15 | 2005-02-10 | Kcm Corp | Sealing material |
WO2008007504A1 (en) * | 2006-07-11 | 2008-01-17 | Nippon Electric Glass Co., Ltd. | Glass composition for sealing and sealed material |
JP2009256183A (en) * | 2008-03-28 | 2009-11-05 | Asahi Glass Co Ltd | Frit |
JP2011518111A (en) * | 2008-04-16 | 2011-06-23 | アルケマ フランス | Method for producing acrolein from glycerin |
CN102432292A (en) * | 2011-09-22 | 2012-05-02 | 郑州大学 | Sintering synthesis method for nanometer negative expansion ceramic Zr2(WO4)(PO4)2 |
CN102433454A (en) * | 2011-09-22 | 2012-05-02 | 郑州大学 | Sintering synthesis method of metal-based ceramic material Al-Zr2P2WO12 having controllable thermal expansion coefficient |
JP2014019628A (en) * | 2012-07-20 | 2014-02-03 | Taiheiyo Cement Corp | Low thermal expansion ceramic, stage for exposure equipment, and production method of low thermal expansion ceramic |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4180551A (en) * | 1971-04-08 | 1979-12-25 | Texas A&M University System | Modified zirconium phosphates |
JP4791872B2 (en) * | 2006-03-30 | 2011-10-12 | 株式会社ノリタケカンパニーリミテド | Conductive paste |
CN100358833C (en) * | 2006-04-25 | 2008-01-02 | 武汉理工大学 | Method for preparing ceramic material of zirconium phosphate |
CN101891470B (en) * | 2010-06-21 | 2012-07-11 | 郑州大学 | Sintering and synthesizing method of negative thermal expansion material Zr2P2MO12 |
KR101263086B1 (en) * | 2010-12-28 | 2013-05-09 | 주식회사 포스코 | Plate type zirconium phosphate and preparation method thereof |
CA2910589C (en) * | 2013-05-03 | 2020-11-10 | Fmc Kongsberg Subsea As | Elastomeric seal |
JP6179031B2 (en) | 2013-06-27 | 2017-08-16 | 日本特殊陶業株式会社 | Negative expansion ceramics |
CN104844201A (en) * | 2015-06-09 | 2015-08-19 | 哈尔滨工业大学 | Method for preparing zirconium oxide/zirconium tungstate composite material by utilizing crystal form stabilized zirconium oxide as raw material |
WO2017061402A1 (en) * | 2015-10-07 | 2017-04-13 | 日本化学工業株式会社 | Production method for zirconium tungsten phosphate |
-
2016
- 2016-09-30 JP JP2016193026A patent/JP6190023B1/en active Active
- 2016-09-30 JP JP2016192427A patent/JP6105140B1/en active Active
- 2016-10-04 KR KR1020187008487A patent/KR102070738B1/en active IP Right Grant
- 2016-10-04 US US15/763,627 patent/US10167197B2/en active Active
- 2016-10-04 KR KR1020187008500A patent/KR102611412B1/en active IP Right Grant
- 2016-10-04 EP EP16853557.3A patent/EP3360848B1/en active Active
- 2016-10-04 CN CN201680055927.2A patent/CN108137325B/en active Active
- 2016-10-04 CN CN201680055928.7A patent/CN108025915B/en active Active
- 2016-10-04 US US15/759,333 patent/US10280086B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002517377A (en) * | 1998-05-19 | 2002-06-18 | コーニング インコーポレイテッド | Negative intumescent material, method for its preparation and use |
JP2005035840A (en) * | 2003-07-15 | 2005-02-10 | Kcm Corp | Sealing material |
WO2008007504A1 (en) * | 2006-07-11 | 2008-01-17 | Nippon Electric Glass Co., Ltd. | Glass composition for sealing and sealed material |
JP2009256183A (en) * | 2008-03-28 | 2009-11-05 | Asahi Glass Co Ltd | Frit |
JP2011518111A (en) * | 2008-04-16 | 2011-06-23 | アルケマ フランス | Method for producing acrolein from glycerin |
CN102432292A (en) * | 2011-09-22 | 2012-05-02 | 郑州大学 | Sintering synthesis method for nanometer negative expansion ceramic Zr2(WO4)(PO4)2 |
CN102433454A (en) * | 2011-09-22 | 2012-05-02 | 郑州大学 | Sintering synthesis method of metal-based ceramic material Al-Zr2P2WO12 having controllable thermal expansion coefficient |
JP2014019628A (en) * | 2012-07-20 | 2014-02-03 | Taiheiyo Cement Corp | Low thermal expansion ceramic, stage for exposure equipment, and production method of low thermal expansion ceramic |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11384024B2 (en) | 2018-06-26 | 2022-07-12 | Nippon Chemical Industrial Co., Ltd. | Negative thermal expansion material, manufacturing method and composite material thereof |
CN117246990A (en) * | 2023-11-16 | 2023-12-19 | 合肥国轩高科动力能源有限公司 | Lithium iron manganese phosphate, preparation method thereof and lithium ion battery |
CN117246990B (en) * | 2023-11-16 | 2024-03-05 | 合肥国轩高科动力能源有限公司 | Lithium iron manganese phosphate, preparation method thereof and lithium ion battery |
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EP3360848A4 (en) | 2019-04-24 |
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US20180265358A1 (en) | 2018-09-20 |
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CN108137325B (en) | 2021-09-24 |
CN108025915A (en) | 2018-05-11 |
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